Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein

ABSTRACT

Provided are microbiocidal solutions comprising an aryl alkanol solvent and a microbiocidal compound dissolved therein. The solutions may be used to impart microbiocidal properties to polymer compositions.

This is a divisional of co-pending application Ser. No. 619,092 filed onJun. 11, 1984, now U.S. Pat. No. 4,663,077.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to liquid microbiocidal solutions containing anaryl alkanol and a microbiocidal compound dissolved in said arylalkanol.

This invention also relates to compositions comprising a polymerprocessing aid and a microbiocidal compound dissolved in an arylalkanol.

The present invention further relates to a process for impartingmicrobiocidal properties to polymer compositions comprising adding tothe polymer composition a liquid microbiocidal solution comprising anaryl alkanol and a microbiocidal compound dissolved therein.

This invention also relates to a process for imparting microbiocidalproperties to a polymer composition comprising adding to the polymercomposition a composition comprising a polymer processing aid and amicrobiocidal compound which is present in the polymer processing aid asthe solute in an aryl alkanol solvent.

This invention further relates to compositions comprising a solution ofa liquid plasticizer for vinyl resins and a microbiocidal amount of amicrobiocidal compound dissolved in an aryl alkanol.

This invention further relates to vinyl resin compositions comprising anadmixture of a vinyl resin and a vinyl resin plasticizer containing, inan amount sufficient to impart microbiocidal properties to the vinylresin composition, a microbiocidal compound dissolved in an arylalkanol.

2. Prior Art

It is presently common practice to protect polymer or plasticcompositions from microbial, e.g. bacterial or fungal, attack byincorporating a microbiocidal composition into the polymer or plastic.The resulting polymer compositions prevent the deterioration of articlesformed from the polymer compositions due to microbiological attack onthe plasticizers or other polymer additives which are normallyincorporated into the polymer to impart desirable physical properties tothe article and to facilitate forming of the article.

Many of the available microbiocidal materials are solid and, in order toincorporate them homogeneously in the polymer composition, it isnecessary to first mix them with a liquid which solubilizes or dispersesthe material uniformly and thereafter, mix the thus-formed liquidcomposition with the polymer. Unfortunately, the solubility of many ofthe microbiologically active materials in the more common solventmaterials is quite low. Therefore, it is either difficult to incorporatea sufficiently high concentration of the microbiocidal material with thepolymer or, if sufficiently high concentrations of the microbiocidalmaterial can be incorporated in the polymer, an undesirably highconcentration of the solvent must also be incorporated in the polymerwith the resultant deterioration of the desirable characteristics of thepolymer composition.

Attempts to solve these problems have met with varying, often limited,success. For example, U.S. Pat. No. 3,288,674 issued Nov. 29, 1966 toYeager and U.S. Pat. No. 3,689,449 issued Sept. 5, 1972 to Yeager andWilson disclose the use of solvents having a labile hydrogen, preferablynonyl phenol, to dissolve microbiocidally active phenoxarsine compounds,the resulting solution being subsequently incorporated into resincompositions. Unfortunately, the solubility of the phenoxarsine in nonylphenol is limited to low concentrations which necessitates incorporatingnonyl phenol in the resin at higher concentrations than desirable inorder to attain the desired phenoxarsine levels in the resin.

U.S. Pat. No. 3,360,431 issued December 1967 to Yeager discloses the useof labile hydrogen-containing solvents, preferably nonyl phenol, todissolve microbiocidally active arsenobenzene compounds for subsequentaddition to resin compositions.

U.S. Pat. No. 4,049,822 issued Sept. 20, 1977 to Rei and Wilsondiscloses microbiocidal phenoxarsines dissolved in glycyl phosphites orglycyl phosphonates, the resulting solution being subsequentlyincorporated into resin compositions.

SUMMARY OF THE INVENTION

In accordance with the present invention there are provided liquidmicrobiocidal solutions comprising an aryl alkanol and a microbiocidalcompound dissolved therein.

Also provided in accordance with this invention are compositionscomprising a polymer processing aid and, in an amount at leastsufficient to impart microbiocidal properties to the composition, amicrobiocidal compound which is present in the polymer processing aid asthe solute in an aryl alkanol solvent.

There is also provided in accordance with the present invention aprocess for imparting microbiocidal properties to a polymer compositioncomprising adding to the polymer composition a liquid microbiocidalsolution comprising an aryl alkanol and, in an amount sufficient toimpart microbiocidal properties to the polymer composition, amicrobiocidal compound dissolved therein. This invention also includesthe product produced by this process.

There is further provided in accordance with this invention a processfor imparting microbiocidal properties to a polymer compositioncomprising adding to the polymer composition a composition comprising apolymer processing aid and, in an amount at least sufficient to impartmicrobiocidal properties to the polymer composition, a microbiocidalcompound which is present in the polymer processing aid as the solute inan aryl alkanol solvent. The product of this process is also included inthe invention.

There are also provided in accordance with this invention compositionscapable of plasticizing vinyl resins and imparting microbiocidalproperties thereto, said compositions comprising a liquid plasticizerfor vinyl resins and in an amount sufficient to impart microbiocidalproperties to the plasticizing composition a microbiocidal compoundpresent in the plasticizer as the solute in an aryl alkanol solvent,said solute and solvent being a liquid uniformly distributed in saidplasticizer to form a single phase system.

There are further provided in accordance with this invention vinyl resincompositions comprising an admixture of vinyl resin and a vinyl resinplasticizer, said vinyl resin composition containing, in an amountsufficient to impart microbiocidal properties to said vinyl resincomposition, a microbiocidal compound present in said plasticizer as thesolute in an aryl alkanol solvent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The aryl alkanols useful as solvents in the practice of this inventionare compounds which have an hydroxyl group attached to an aromatic ringthrough an alkylene group. That is, the aryl alkanols of this inventioncontain an aromatic ring to which is attached a group having the formula--R--OH where R is a straight or branched-chain alkylene group,preferably having 1-6 carbon atoms, more preferably 1-3 carbon atoms andmost preferably 1 carbon atom. The alkylene group may be unsubstitutedor substituted with other groups such as, for example, halogens, amines,methyl, hydroxyl, or alkoxy groups.

The term aryl as used herein refers to aromatic rings which may besubstituted with functional groups. Examples of such aromatic ringsinclude, but are not limited to, benzene, naphthalene, and biphenylrings. When the aryl group is substituted with functional groups, it mayhave any number of groups attached to the aromatic ring, it beingrequired only that the type of functional groups, their position on thering and/or their number does not interfere with the aryl alkanol'sability to dissolve the microbiocidal compound or, if it is to beemployed as part of a polymer composition, its compatibility with thepolymer. Examples of such functional groups on the aryl rings include,but are not limited to, halogen, aryloxy, amino, hydroxyl, alkoxyl, andnitro groups.

The aryl alkanols useful in the practice of this invention may befurther defined by the following general formula: ##STR1## wherein A isan aromatic ring, preferably benzene, which may be unsubstituted, e.g.phenyl, or substituted with one or more halo, aryloxy, amino, hydroxyl,alkoxyl or nitro groups, and R is a straight or branched chain alkylenegroup, preferably having 1-6 carbon atoms, which may be unsubstituted orsubstituted with halo, amino, methyl, hydroxyl or alkoxyl groups.

The aryl alkanols which are useful in the practice of the presentinvention are those in which the hydroxyl group of the alkanol is aprimary, secondary or tertiary alcohol. The preferred aryl aklanols arethose in which the hydroy group is a primary alcohol.

Examples of aryl alcohols which may be employed in accordance with thisinvention include, but are not limited to, the following: ##STR2## Ofthese aryl alkanols, benzyl alcohol, 2,4-dichlorobenzyl alcohol, andstyralyl alcohol are preferred, benzyl alcohol being especiallypreferred.

The aryl alkanols exemplified above are all liquids with the exceptionof 2,4-dichlorobenzyl alcohol, which is a solid. This compound has quitesurprisingly been found to act as a solvent (or co-solvent) for thosemicrobiocidal compounds which are liquids. If the 2,4-dichlorobenzylalcohol is heated slightly it melts and then can be combined with theliquid microbiocidal compound to form a stable solution. The2,4-dichlorobenzyl alcohol also exhibits microbiocidal activity byitself. Thus, it can be dissolved in another aryl alkanol, for examplebenzyl alcohol, to produce a microbiocidal solution in accordance withthis invention.

A wide variety of microbiocidal compounds are useful in the practice ofthis invention. In general, the useful microbiocidal compounds possessmicrobiocidal activity and are soluble in an aryl alkanol. If the arylalkanol/microbiocidal compound solution is to be employed incompositions containing polymer processing aids and/or polymers, themicrobiocidal compound should be compatible with such processing aids orpolymers.

Examples of the types of microbiocidal compounds which may be employedin this invention include, but are not limited to, phenoxarsines(including bisphenoxarsines), phenarsazines (including bispenarsazines),maleimides, isoindole dicarbximides, having a sulfur atom bonded to thenitrogen atom of the dicarboximide group, halogenated aryl alkanols andisothiazolinone compounds.

The microbiocidal phenoxarsine and phenarsazine compounds useful in thecompositions of this invention include compounds represented by theformulas: ##STR3## Where X is halogen or thiocyanate, Y is oxygen orsulfur, Z is oxygen or nitrogen, R is halo or lower alkyl, and n is 0 to3.

Examples of these phenoxarsines and phenarsazines include, but are notlimited to, 10-chlorophenoxarsine; 10-iodophenoxarsine;10-bromophenoxarsine; 4-methyl-10-chlorophenoxarsine;2-tert-butyl-10-chlorophenoxarsine; 1,4-dimethyl-10-chlorophenoxarsine;2-methyl-8,10-dichlorophenoxarsine; 1,3,10-trichlorophenoxarsine;2,6,10-trichlorophenoxarsine; 1,2,4,10-tetrachlorophenoxarsine;10,10'-oxybisphenoxarsine (OBPA); 10-thiocyanato phenoxarsine; and 10,10'-thiobisphenoxarsine; 10,10'-oxybisphenarsazine and10,10'-thiobisphenarsazine.

The microbiocidal maleimide compounds useful in the compositions of thisinvention are exemplified by a preferred maleimide, N-(2-methylnaphthyl)maleimide.

The microbiocidal compounds useful in the practice of this inventionwhich are isoindole dicarboximides having a sulfur atom bonded to thenitrogen atom of the dicarboximide group are compounds which contain atleast one group having the structure: ##STR4## The preferred isoindoledicarboximides are the following: ##STR5## bis-N-[(1, 1, 2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide ##STR6##N-trichloromethylthio-4-cyclohexene-1, 2-dicarboximide ##STR7##N-trichloromethylthio phthalimide

The halogenated aryl alkanols which can be used as microbiocidalcompounds in accordance with this invention are exemplified by apreferred compound, 2,4-dichlorobenzyl alcohol.

An example of a preferred isothiazolinone compound useful in thecomposition of this invention is 2-(n-octyl-4-isothiazolin-3-one).

The most preferred microbiocidal compounds are the bisphenoxarsines andbisphenarsazines having the formula: ##STR8## where Y is oxygen orsulfur and Z is oxygen or nitrogen. Of these bisphenoxarsines andbisphenarsazines, the most preferred are 10, 10'-oxybisphenoxarsine; 10,10'-thiobisphenoxarsine; 10, 10'-oxybisphenarsazine; and 10,10'-thiobisphenarsazine.

The microbiocidal compositions useful in this invention should beemployed in an amount at least sufficient to impart microbiocidalproperties to the composition or material containing them. This amountcan vary widely depending upon the particular microbiocidal compoundemployed, the other components of the composition in which it isemployed, the environment in which it will function and several otherfactors. The minimum amount of microbiocidal compound employed will bedetermined by what is known in the art as its Minimum InhibitoryConcentration (MIC). The maximum amount of microbiocidal compound whichcan be employed is determined only by the amount of microbiocidalcompound which can be uniformly incorporated into a particularcomposition without adversely affecting the physical properties of thecomposition. In general, the compositions of this invention whichpossess microbiocidal properties contain from about 50 parts per million(ppm) to about 10,000 ppm, preferably about 100 ppm to 500 ppm, ofmicrobiocidal compound.

The liquid microbiocidal solutions of this invention preferably containmuch more microbiocidal compound than would be necessary simply toimpart the desired microbiocidal properties to them. This is also truefor the polymer processing aid-containing composition. Thesecompositions can contain large amounts of microbiocidal compound sincethey are advantageously employed as "concentrates" to producecompositions which have a lower concentration of microbiocidal compound,but still have the desired degree of microbiocidal activity. Forexample, the liquid microbiocidal solutions may contain from about 0.1about 30 weight percent microbiocidal compound (based on total solutionweight). However, a solution containing, for example, 25% microbiocidalcompound may be used to prepare a polymer processing aid-containingcomposition which contains only about 5% microbiocidal compound, whichpolymer processing aid-containing composition may in turn be used toprepare a polymer composition contain only 100 to 500 ppm microbiocidalcompound.

The microbiocidal solutions of this invention may be employed asadditives for polymer compositions to impart microbiocidal properties tosaid polymer compositions. They may be added either directly to thepolymer composition or they may be first incorporated into a polymerprocessing aid which serves as a carrier for incorporating themicrobiocidal solutions into the polymer composition. When the lattermanner is chosen, the polymer processing aids may be any of a variety ofmaterials which are compatible with the polymer composition andmicrobiocidal solution (e.g. the microbiocidal compound does notprecipitate or otherwise separate from the composition solution whenused with the processing aid). Examples of these polymer processing aidsinclude, but are not limited to, plasticizers, lubricants, and volatileand non-volatile solvents. Specific examples of these processing aidsinclude, but are not limited to, typical plasticizers such as trieresylphosphate, dipropylene glycol dibenzoate, diphenylcresyl phosphate,dipropylene glycol dibenzoate, diphenylcresyl phosphate, epoxidizedsoya, epoxidized tallate, dioctyl azelate, di(2-ethyl hexyl) phthalate,alkyl aryl phosphates,diisobutyl phthalate, diisodecyl phthalate,hydrogenated methyl rosin ester, n-octyl n-decyl phthalte, mixed n-alkylphthalates, butyl benzyl phthalate, di-n-octyl phthalte, di-n-decylphthalte, 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate,trioctyl trimellitate and low molecular weight polymeric plasticizerssuch as Paraplex G-30 plasticizer sold by Rohm & Haas Co. and the like.Of these plasticizers, di(2-ethyl hexyl) phthalate, diisodecylphthalate, butyl benzyl phthalate and epoxidized soya are preferred.Other polymer processing aids useful in this invention include, but arenot limited to, polypropylene glycol; 1,4-butanediol; silicone oils suchas polydimethylsiloxane; and methyl ethyl ketone.

As previously indicated, the concentration of microbiocidal compound inthe microbiocidal solution may be sufficiently high that the polymerprocessing aid-containing composition prepared from said microbiocidalsolution will in turn contain enough micro-biocidal compound that, whenthe polymer processing aid-containing composition is added to a polymer,the ultimately-formed polymer composition and articles preparedtherefrom will have microbiocidal properties. It is in this aspect ofthe invention where the solvents employed in the practice of the presentinvention are particularly advantageous. The aryl alkanols of thisinvention are capable of forming microbiocidal solutions which willproduce polymer processing aid-containing compositions containingconcentrations of microbiocidal compounds significantly higher thancould be achieved with prior art solvents. For example, heretoforeOBPA-containing plasticizing compositions contained a maximum of about2% weight OBPA based on the weight of the plasticizing composition. Ithas now been quite unexpectedly found that the aryl alkanols of thisinvention are capable of producing OBPA-containing plasticizingcompositions containing at least 5% by weight OBPA based on the weightof the plasticizing composition.

This unexpected ability of the aryl alkanols to produce polymerprocessing aid-containing compositions containing high levels ofmicrobiocidal compound leads to several very significant advantages. Forexample, shipping and handling cost savings are achieved because more"active ingredient" (the microbiocidal compound) can now be dissolved ina given amount of polymer processing aid-containing composition. Statedanother way, for a given amount of microbiocidal compound, less "inertingredients" (solvent and polymer processing aid) are required toproduce a polymer processing aid-containing composition, resulting inraw material cost savings. Also, because less inert ingredients areneeded, handleing and shipping costs are lower.

The polymer processing aid-containing compositions of this inventionalso minimize the potential effects of the solvent for the microbiocidalcompounds on polymer formulations containing them. Because less solventis required to prepare a polymer processing aid-containing compositioncontaining a given level of microbiocidal compound, less solvent isintroduced into the polymer formulation. Therefore, if the solvent isnot entirely compatible with the other components of the polymerformulation, the negative effects of that incompatibility will beminimized.

Apart from their ability to dissolve more microbiocidal compound, thearyl alkanols of this invention also have the surprising advantage ofproducing polymer processing aid-containing compositions which are lowin odor and less irritating compared to the solvents disclosed in theprior art such as nonyl phenol and phosphites.

It has also been quite surprisingly discovered that the microbiocidalsolutions of the present invention can often be prepared at temperaturesconsiderably lower than those required with the solvents of the priorart. For example, in order for nonyl phenol to dissolve OBPA, a nonylphenol/OBPA mixture must generally be heated to about 300° F. However, abenzyl alcohol/OBPA solution according to the present invention may beprepared by heating to only about 140° F. Obviously, when large massesof material are required to be heated, as in a commercial operation, thelower temperature requirement of the microbiocidal solutions of thisinvention can result in tremendous energy savings. The lower temperaturealso helps prevent undesirable chemical reactions (such as the oxidationof benzyl alcohol to benzaldehyde) from occurring.

The polymers employed in the processes and products of this inventioncover a wide variety of materials. In general, they includethermoplastic and thermosetting polymers, elastomers and other materialscommonly known as "plastics". Other organic materials, for instancenaturally occurring materials such as natural rubbers, cellulose and thelike are considered full equivalents of the "polymers" of this inventionand should be included within that term. Examples of the polymers usefulin the practice of this invention include, but are not limited to vinylresins (such as those made from vinyl chloride and/or vinyl esters)polyolefins (such as polyethylene and polypropylene), elastomericpolyurethanes, nylon, polystyrene, polyesters (such as polyethyleneterephthalate), polycarbonates, acrylonitrile-butadiene-styrene (ABS)copolymers, SBR rubbers, styrene-acrylonitrile copolymers, acrylicpolymers, thermosetting polyurethanes (such as those used for foams andcoatings), phenolic resins, silicone rubbers, natural rubber, EDPMpolymers, cellulose and its derivatives, epoxy resins and variouslatexes.

The microbiocidal solutions of this invention can be prepared by simplyadding the desired amount of microbiocidal compound to the aryl alkanolsolvent, heating the resulting mixture to a temperature which will causethe microbiocidal compound to dissolve, and maintaining that temperatureuntil all of the microbiocidal compound dissolves. The resultingsolution can then be cooled to room temperature. In this manner, stablemicrobiocidal solutions, i.e. those wherein no significant amount ofmicrobioidal compound precipitates from the solution upon cooling toroom temperature, can be formed containing up to about 30% by weightmicrobiocidal compound based on the weight of the resultingmicrobiocidal solution.

The polymer processing aid-containing compositions of the presentinvention may be prepared by merely adding the polymer processing aid toa microbiocidal solution prepared as described above and mixing at roomtemperature until a uniform solution results. Alternatively, allingredients of the polymer processing aid-containing composition(microbiocidal compound, aryl alkanol and polymer processing aid) can bemixed together and heated until the microbiocidal compound dissolves.

The microbiocidal solutions of this invention can be used to impartmicrobiocidal properties to polymer compositions. This can be done bysimply adding the microbiocidal solution, either alone or as part of apolymer processing aid-containing composition, to the polymercomposition by any of several convenient methods known in the art. Thus,for instance, the polymer composition can be melted and themicrobiocidal solution or polymer processing aid-containing compositionadded to and mixed with it (as in an extruder). Alternatively, thepolymer can be softened with or dissolved in a solvent and themicrobiocidal solution or polymer processing aid-containing compositionadded to and mixed therewith.

The following examples illustrate the present invention, and are notintended to limit the invention or its scope in any manner. As used inthe examples and throughout this specification, all parts andpercentages all by weight unless otherwise indicated.

EXAMPLE 1

Several microbiocidal solutions were prepared by mixing themicrobiocidal compounds and solvents indicated in Table I and heatingthe resulting mixtures at the temperatures indicated in Table I untilthey became clear. (the numbers in parentheses indicate the weightpercent of each ingredient based on solution weight). The resultingclear solutions were then cooled to room temperature and aged at roomtemperature (RT) for varying periods of time, after which they wereexamined to determine whether the microbiocidal compound was still insolution.

EXAMPLE 2

Polymer processing aid-containing compositions were prepared by firstpreparing a solution of microbiocidal compound in an aryl alkanolsolvent as described in the foregoing examples, blending the thus-formedsolution with a polymer processing aid and heating the blend whilestirring until thoroughly mixed. Several polymer processingaid-containing compositions were prepared in this manner using theingredients and conditions indicated in Table II with the results alsoindicated in Table II. All percentages in Table II are by weight percentbased on the total weight of the compositions.

                                      TABLE I                                     __________________________________________________________________________                                              SOLUBILITY.sup.5                    SOLUTION                                                                             MICROBIOCIDAL           TEMP.      AFTER   AFTER  AFTER                NO.    COMPOUND   SOLVENT      (°C.)                                                                         RT  24 HOURS RT                                                                           7 DAYS                                                                               1 MO.                __________________________________________________________________________                                                             RT                                                  (93° C.)                                F      OBPA(28.6%)                                                                              benzyl alcohol                                                                             S      S   --      S      --                                     (71.4%)                                                     K      OBPA(27.0%)                                                                              benzyl alcohol                                                                             "      "   --      S      --                                     (73.0%)                                                     I      OBPA(25.0%)                                                                              benzyl alcohol                                                                             "      "   --      S      --                                     (75.0%)                                                     J      OBPA(20.0%)                                                                              benzyl alcohol                                                                             "      "   --      S      --                                     (80.0%)                                                                                    (71-104° C.)                            1      OBPA(20.0%)                                                                              styralyl alcohol                                                                           S      S   S       --     MP                                     (80.0%)                                                     2      OBPA(20.0%)                                                                              phenethyl alcohol                                                                          "      "   S       --     S                                      (80.0%)                                                     3      OBPA(20.0%)                                                                              3-phenyl-1-propanol                                                                        "      "   S       --     S                                      (80.0%)                                                     5      OBPA(20.0%)                                                                              m-phenoxy benzyl alcohol                                                                   "      "   S       --     S                                      (80.0%)                                                     7      OBPA(20.0%)                                                                              benzyl alcohol                                                                             "      "   S       --     S                                      (80.0%)                                                     A      RH-893.sup.1 (10.0%)                                                                     benzyl alcohol                                                                             "      "   S       S      --                                     (90.0%)                                                     B      ATV-129.sup.2 (10.0%)                                                                    benzyl alcohol                                                                             "      "   SP      SP     --                                     (90.0%)                                                     C      Myacide SP.sup.3 (10.0%)                                                                 benzyl alcohol                                                                             "      "   S       S      --                                     (90.0%)                                                     D      Vancide 89.sup.4 (10.0%)                                                                 benzyl alcohol                                                                             "      "   SP      SP     --                                     (90.0%)                                                     H      OBPA(10.0%)                                                                              benzyl alcohol                                                                             "      "   S       S      --                                     (90.0%)                                                     __________________________________________________________________________     .sup.1 2(n-octyl)-4-isothiazolin-3-one                                        .sup.2 N--(2methyl-1-naphthyl) maleimide                                      .sup.3 2,4dichlorobenzyl alcohol                                              .sup.4 N--trichloromethyl thio4-cyclohexene-1,2-dicarboximide                 .sup.5 S = soluble                                                            SP = slight precipitate                                                       MP = medium precipitate                                                  

                                      TABLE II                                    __________________________________________________________________________    MICRO-                             % MICROB.    SOLUBILITY                         BIOCIDAL                      CMPD. IN     AFTER                                                                              AFTER                                                                              AFTER               COMP.                                                                              COMPOUND       PLASTICIZER                                                                            HEATED                                                                              PLAST.       24 HRS                                                                             7 DAYS                                                                             1 MO.               NO.  (%)     SOLVENT                                                                              (%)      AT (°C.)                                                                     COMP'N HOT                                                                              RT RT   RT   RT                  __________________________________________________________________________    V-11 OBPA    None   DIDP.sup.6                                                                             104° C.                                                                      5%     S  S  HP.sup.9                                                                           HP   HP                  (Control)                                                                     V-1  Sol'n 1-Table I                                                                              "        "     5%     S  S  S    S    SP                  V-2  Sol'n 2-Table I                                                                              "        "     5%     S  S  S    S    S                   V-3  Sol'n 3-Table I                                                                              "        "     5%     S  S  S    S    S                   V-5  Sol'n 5-Table I                                                                              "        "     5%     S  S  S    S    S                   V-7  Sol'n 7-Table I                                                                              "        "     5%     S  S  S    S    S                   58   Sol'n J-Table I                                                                              DOP.sup.7                                                                              RT    5%     S  S  --   S    --                  59   "              DIDP     "     5%     S  S  --   S    --                  60   "              ESO.sup.8                                                                              "     5%     S  S  --   S    --                  61   "              DOP      "     4%     S  S  --   S    --                  62   "              DIDP     "     4%     S  S  --   S    --                  63   "              ESO      "     4%     S  S  --   S    --                  64   Sol'n I-Table I                                                                              DOP      "     5%     S  S  --   S    --                  65   "              DIDP     "     5%     S  S  --   S    --                  66   "              ESO      "     5%     S  S  --   S    --                  67   "              DOP      "     4%     S  S  --   S    --                  68   "              DIDP     "     4%     S  S  --   S    --                  69   "              ESO      "     4%     S  S  --   S    --                  70   Sol'n F-Table I                                                                              DOP      "     5%     S  S  --   S    --                  71   "              DIDP     "     5%     S  S  --   S    --                  72   "              ESO      "     5%     S  S  --   S    --                  73   "              DOP      "     4%     S  S  --   S    --                  74   "              DIDP     "     4%     S  S  --   S    --                  75   "              ESO      "     4%     S  S  --   S    --                  76   Sol'n K-Table I                                                                              DOP      "     5%     S  S  --   S    --                  77   "              DIOP     "     5%     S  S  --   S    --                  78   "              ESO      "     5%     S  S  --   S    --                  W-1A OBPA(1.0%)                                                                            BA.sup.19 (2.0%)                                                                     ESO(97%)  49° C.                                                                      1%     S  S  --   --   --                  W-1B "       "      DOP(97%) "     1%     S  S  --   --   --                  W-1C "       "      ODP.sup.10 (97%)                                                                       "     1%     S  S  --   --   --                  W-2A OBPA(1.0%)                                                                            BA(4%) ESO(95%) "     1%     S  S  --   --   --                  W-2B "       "      DOP(95%) "     1%     S  S  --   --   --                  W-2C "       "      ODP(95%) "     1%     S  S  --   --   --                  W-2D "       "      MAP.sup.11 (95%)                                                                       "     1%     S  S  --   --   --                  W-3  OBPA(2.0%)                                                                            BA(8.0%)                                                                             ESO(90%) "     2%     S  S  --   --   --                  W-4  "       "      DOP(90%) "     2%     S  S  --   --   --                  W-5  "       "      DIDP(90%)                                                                              "     2%     S  S  --   --   --                  W-6  CBPA(3.0%)                                                                            BA(12.0%)                                                                            ESO(85%) "     3%     SP SP --   --   --                  W-7  "       "      DOP(85%) "     3%     SP SP --   --   --                  W-8  "       "      DIDP(85%)                                                                              "     3%     SP SP --   --   --                  W-9  OBPA(1.0%)                                                                            BA(5.0%)                                                                             ESO(94%) 149° C.                                                                      1%     S  S  --   --   --                  W-10 "       "      DOP(94%) "     1%     SP S  --   --   SP                  W-11 "       "      DIDP(94%)                                                                              "     1%     SP S  --   --   SP                  W-12 OBPA(2.0%)                                                                            BA(5.0%)                                                                             ESO(93%) "     2%     SP S  S    --   MP                  W-13 "       "      DOP(93%) "     2%     SP S  --   --   MP                  W-14 "       "      DIDP(93%)                                                                              "     2%     SP S  --   --   MP                  W-15 OBPA(1.0%)                                                                            BA(4.0%)                                                                             DOZ.sup.12 (95%)                                                                       "     1%     S  S  --   --   S                   W-16 "       "      LT.sup.13 (95%)                                                                        "     1%     S  S  --   --   S                   W-17 OBPA(2.0%)                                                                            BA(8.0%)                                                                             DOZ(90%) "     2%     S  S  --   --   S                   W-18 "       "      LT(90%)  "     2%     S  S  --   --   S                   W-19 OBPA(3.0%)                                                                            BA(12.0%)                                                                            DOZ(85%) "     3%     S  S  --   --   S                   W-20 "       "      LT(85%)  "     3%     S  S  --   --   S                   W-21 OBPA(1.0%)                                                                            BA(2.0%)                                                                             DIDP(97%)                                                                              "     1%     S  S  --   --   S                   W-22 OBPA(1.03%)                                                                           BA(1.5%)                                                                             DOP(97.47%)                                                                            "     1.03%  S  S  --   --   S                   W-23 OBPA(1.03%)                                                                           BA(1.0%)                                                                             DOP(97.97%)                                                                            "     1.03%  S  S  --   --   S                   W-24 OBPA(1.03%)                                                                           BA(0.5%)                                                                             DOP(98.47%)                                                                            "     1.03%  S  S  --   --   S                   W-25 OBPA(2.06%)                                                                           BA(2.0%)                                                                             DOP(95.94%)                                                                            "     2.06%  S  S  --   --   S                   W-26 OBPA(3.09%)                                                                           BA(3.0%)                                                                             DOP(93.91%)                                                                            "     3.09%  S  S  --   --   S                   W-27 OBPA(4.12%)                                                                           BA(4.0%)                                                                             DOP(91.88%)                                                                            "     4.12%  S  S  --   --   S                   W-28 OBPA(1.03%)                                                                           BA(2.0%)                                                                             DIDP(96.97%)                                                                           "     1.03%  S  S  --   --   S                   W-29 OBPA(1.03%)                                                                           BA(1.5%)                                                                             DIDP(97.47%)                                                                           "     1.03%  S  S  --   --   S                   W-30 OBPA(1.03%)                                                                           BA(1.0%)                                                                             DIDP(97.97%)                                                                           "     1.03%  S  S  --   --   S                   W-31 OBPA(1.03%)                                                                           BA(0.5%)                                                                             DIDP(98.47%)                                                                           "     1.03%  S  S  --   --   S                   W-32 OBPA(2.06%)                                                                           BA(2.0%)                                                                             DIDP(95.94%)                                                                           "     2.06%  S  S  --   --   S                   W-33 OBPA(3.09%)                                                                           BA(3.0%)                                                                             DIDP(93.91%)                                                                           "     3.09%  S  S  --   --   S                   W-34 OBPA(4.12%)                                                                           BA(4.0%)                                                                             DIDP(91.88%)                                                                           "     4.12%  S  S  --   --   S                   W-35 OBPA(3.09%)                                                                           BA(3.0%)                                                                             ESO(93.91%)                                                                            "     3.09%  S  S  --   --   S                   W-36 OBPA(4.12%)                                                                           BA(4.0%)                                                                             ESO(91.88%)                                                                            "     4.12%  S  S  --   --   S                   W-37 OBPA(2.06%)                                                                           BA(8.0%)                                                                             G-30.sup.14 (89.94%)                                                                   "     2.06%  S  S  --   --   S                   W-38 "       "      Erla.sup.15 (89.94%)                                                                   "     2.06%  S  S  --   --   S                   W-39 "       "      TOTM.sup.16 (89.94%)                                                                   "     2.06%  S  S  --   --   S                   W-40 "       "      DOZ(89.94%)                                                                            "     2.06%  S  S  --   --   S                   W-41 "       "      BBP.sup.17 (89.94%)                                                                    "     2.06%  S  S  --   --   S                   W-42 OBPA(2.0%)                                                                            BA(8.0%)                                                                             DODP.sup.18 (90%)                                                                      "     2.0%   S  S  --   --   S                   W-43 OBPA(2.06%)                                                                           BA(4.0%)                                                                             ESO(93.94%)                                                                            116° C.                                                                      2.06%  S  S  --   --   S                   W-44 OBPA(2.06%)                                                                           BA(3.0%)                                                                             ESO(94.94%)                                                                            127° C.                                                                      2.06%  S  S  --   --   S                   W-45 OBPA(2.05%)                                                                           BA(1.0%)                                                                             ESO(96.94%)                                                                            149° C.                                                                      2.06%  S  S  --   --   S                   __________________________________________________________________________     .sup.6 DIDP is diisodecyl phthalate                                           .sup.7 DOP is di(2ethyl hexyl) phthalate                                      .sup.8 ESO is epoxidized soya                                                 .sup.9 Heavy precipitate                                                      .sup.10 ODP is noctyl ndecyl phthalate                                        .sup.11 MAP is mixed nalkyl 6-10 phthalate                                    .sup.12 DOZ is dioctyl azelate                                                .sup.13 LT is Plastolein 9066 Lt. low temp. plasticizer sold by Emery         Industries, Inc.                                                              .sup.14 G30 is Paraplex. G30 low mol. wt. polymeric plasticizer sold by       Rohm & Haas Co.                                                               .sup.15 Erla is 3,4epoxycyclohexyl methyl 3,4epoxycyclohexane carboxylate     .sup.16 TOTM is trioctyltrimellitate                                          .sup.17 BBP is butyl benzyl phthalate sold as Santicizer S160 by Monsanto     Industrial Chemicals Co.                                                      .sup.18 DODP is din-octyl ndecyl phthalate sold as Santicizer 711 by          Monsanto Industrial Chemicals Co.                                             .sup.19 BA is benzyl alcohol                                             

EXAMPLE 3

Several of the compositions shown in Table I and Table II were subjectedto aging (storage stability) tests by aging the sample at roomtemperature for seven days, after which they were subjected to fivefreeze-thaw cycles. Each freeze-thaw (F-T) cycle consisted of storingthe sample in a freezer at 0° F. for two days followed by one day atroom temperature. After five of these cycles the samples were examinedfor stability with the following results:

                  TABLE III                                                       ______________________________________                                        Solution or      Stability after                                                                          Stability after                                   Plasticizing Comp'n No.                                                                        7 days RT  5 F-T cycles                                      ______________________________________                                        F                Stable     Not Stable                                        K                Stable     Not Stable                                        I                Stable     Stable                                            J                Stable     Stable                                            58 thru 78       Stable     Stable                                            ______________________________________                                    

It should be emphasized that those compositions in Table III which werenot stable after the F-T cycles are still quite useful in the practiceof this invention. For instance, they can be used to prepare polymerprocessing aid-containing compositions which are stable after F-Tcycles, or can be stored and used under conditions which avoid F-Tcycles.

EXAMPLE 4

Compositions W-1A through W-45 from Table II were also subjected to heatstability tests by adding the composition to a poly (vinyl chloride)plastisol in an amount such that the resulting composition contained 5%by weight plasticizing composition, and forming a film from theresulting composition. This film was then divided into several samplesand placed in an oven at about 177° C. Samples were then removed fromthe oven at five minutes intervals for 40 minutes and examined for heatstability. All of the films tested were heat stable.

EXAMPLE 5

A typical plasticizing composition according to this invention wastested to determine whether the aryl alkanol solvent contained thereinhad any adverse effect when the plasticizing composition is employed ina vinyl resin. The plasticizing composition was prepared by heating thefollowing ingredients to about 160° C.

    ______________________________________                                        PLASTICIZING COMPOSITION                                                      INGREDIENTS      WT %                                                         ______________________________________                                        OBPA             3.41                                                         Benzyl alcohol   5.50                                                         DIDP plasticizer 91.09                                                        ______________________________________                                    

This plasticizing composition was incorporated into a typicalplasticized poly (vinyl chloride) dry blend formulation which containedthe following.

    ______________________________________                                        PVC DRY BLEND FORMULATION                                                     INGREDIENT       AMOUNT (gms)                                                 ______________________________________                                        PVC              1500.0                                                       DOP plasticizer  600.0                                                        Heat stabilizer  90.0                                                         Stearic acid lubricant                                                                         3.75                                                         Total            2,193.75 gms                                                 ______________________________________                                    

The plasticizing composition was used in an amount so that the OBPA waspresent in the PVC dry blend formulation at the recommended level ofabout 500 parts per million. The resulting PVC dry blend containing theplasticizing composition was processed on a two-roll mill forapproximately 15 minutes at about 162° C. During this time, the moltenplastic was observed for heat stability, processing characteristics,excessive fuming of the benzyl alcohol, and irritation to the milloperator. No unusual processing difficulties, such as sticking to themill of failure to flux or form a sheet on the hot rollers, wereobserved. The formulation showed no signs of degradation or excessivefuming. No irritation or odor was observed during processing. Thus, thisexample demonstrates that benzyl alcohol does not adversely affect theprocessing of typical plastic materials.

EXAMPLE 6

Antimicrobial efficacy was tested by preparing PVC films as described inExample 5 which contained a polymer processing aid-containingcomposition according to this invention which contained the followingingredients:

    ______________________________________                                        PLASTICIZING COMPOSITION                                                      INGREDIENT       WT %                                                         ______________________________________                                        OBPA             3.41                                                         Benzyl alcohol   5.50                                                         DIDP             91.09                                                        ______________________________________                                    

A control was also made in like manner, except that it contained noantimicrobial compound.

Round samples (1 inch diameter) were cut from the PVC film samples.These round samples were then placed on a glass plate or petri dishwhich was previously coated with agar, innoculated with the testmicroorganism, and placed in an incubator under conditions and for aperiod of time which would normally permit the microorganism to grow onuntreated agar. The dish or plate was then removed and examined forgrowth of the microorganism on the PVC sample.

The results of the above tests are summarized below. The term "Zone ofInhibition" refers the width of an area (measured in millimeters) aroundthe round PVC sample in which no microorganism growth occured on theagar. The "Growth" or "Stain" observations refer to the presence ofmicroorganism growth or stain on the round sample (also called the"contact area").

    ______________________________________                                        SAMPLE                                                                        ______________________________________                                        ZONE OF INHIBITION (mm)/GROWTH                                                FOR STAPH. AUREUS                                                             With plasticizing     8/NGCA                                                  composition                                                                   Control               0/GCA                                                   ZONE OF INHIBITION (mm)/GROWTH                                                FOR K. PNEUMONIAE                                                             With plasticizing     4/NGCA                                                  composition                                                                   Control               0/GCA                                                   ZONE OF INHIBITION(mm)/STAIN FOR PINK STAIN                                   With plasticizing     6/NS                                                    composition                                                                   Control               0/HS                                                    ZONE OF INHIBITION(mm)/GROWTH                                                 FOR MIXED FUNGAL SPORE                                                        With plasticizing     15/NG                                                   composition                                                                   Control               0/TG                                                    ______________________________________                                         NGCA = No Growth in Contact Area                                              GCA = Growth in Contact Area                                                  NS = No Stain                                                                 MS = Moderate Stain                                                           HS = Heavy Stain                                                              NG = No Growth                                                                TG = Trace Growth                                                             LG = Light Growth                                                        

The above data shows that the polymer processing aid-containingcomposition is effective in preventing the growth of microorganisms onthe PVC film.

We claim:
 1. A process for imparting microbiocidal properties to apolymer composition comprising adding to the polymer composition acomprising a polymer processing aid and, in an amount at leastsufficient to impart microbiocidal properties to the polymercomposition, a microbiocidal compound which is present in the polymerprocessing aid as the solute in an aryl alkanol solvent, saidmicrobiocidal compound being selected from the group consisting ofphenoxarsines, phenarsazines, maleimides, isoindole dicarboximideshaving a sulfur atom bonded to the nitrogen atom of the dicarboximidegroup and isothiazolinone compounds.
 2. A process according to claim 1wherein the polymer processing aid is a plasticizer.
 3. A processaccording to claim 2 wherein the plasticizer is selected from the groupconsisting of di(2-ethyl hexyl) phthalate, diisodecyl phthalate, butylbenzyl phthalate and epoxidized soya.
 4. A process according to claim 1wherein the amount of microbiocidal compound is about 50 ppm to about10,000 ppm.
 5. A process according to claim 1 wherein the microbiocidalcompound is selected from the group consisting ofN-(2-methylnaphthyl)maleimide;bis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide;N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide;N-trichloromethylthio phthalimide; 2-(n-octyl-4-isothiazolin-3-one); 10,10'-oxybisphenoxarsine; 10, 10'-thiobisphenoxarsine; 10,10'-oxybisphenarsazine and 10, 10'-thiobisphenoxarsine.
 6. A processaccording to claim 5 wherein the microbiocial compound is10,10'-oxybisphenoxarsine.
 7. A process according to claim 1 wherein thearyl alkanol is benzyl alcohol.
 8. A process according to claim 1wherein the polymer processing aid is a plasticizer, the microbiocidalcompound is 10,10'oxybisphenoxarsine and the aryl alkanol is benzylalcohol.
 9. The product produced by the process of claim
 1. 10. Theproduct produced by the process of claim
 2. 11. The product produced bythe process of claim
 3. 12. The product produced by the process of claim4.
 13. The product produced by the process of claim
 5. 14. The productproduced by the process of claim
 6. 15. The product produced by theprocess of claim
 7. 16. The product produced by the process of claim 8.